1. Field of the Invention
The present invention relates to novel polyazido compounds of the general formulae: including 2-azido-2-azidomethyl-1,3-diazidopropane (1), 2-azidomethyl-2-hydroxy-1,3-diazidopropane (2), 2-azidomethyl-2-nitrato-1,3-diazidopropane (3), 2-azidomethyl-2-nitro-1,3-diazidopropane (4), 2,2-dinitro-1,3-diazidopropane (5), methallyldiazide (6), a dimer of methallyidiazide (6), comprising 3a,8a-Bis-azidomethyl-3a,4,8a,9-tetrahydro-3H,8H-bis[1,2,3]triazolo[1,5-a; 1″,5″-d]pyrazine (6-Dimer), 1,3-diazidoacetone (7), and 2-Oximido-1,3-diazidopropane (8).
Also shown are reaction intermediates of these compounds, including 2,2-bis(chloromethyl)oxirane (9), and 2,2-bis(azidomethyl)oxirane (10).
In addition, a number of potentially useful energetic compounds have been prepared from the low molecular weight polyazido compounds above, including N-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine (7-DNPH), 1,3-Bis(4-carboxytriazolyl)2,2-dinitropropane (12), Tris(4-carboxytriazolomethyl)methanol (13), Benzene-1,3,5-tricarboxylic acid tris(2-azido-1,1-bisazidomethyl-ethyl)ester (14), Adamantane 1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (15), Adamantane carboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester (16), cubane 1,3,5,7-tetracarboxylic acid tetrakis (2-azido-1,1-bisazidomethyl-ethyl)ester (17), cubane 1,4-dicarboxylic acid bis(2-azido-1,1-bisazidomethyl-ethyl)ester (18).
In particular, the present invention relates to novel polyazido carboxylic acid esters.
2. Description of Related Art
Low molecular weight compounds substituted with multiple energetic groups exemplified by azide, nitrato and nitro groups are of interest as energetic plasticizer ingredients, monopropellant formulations and as building blocks for energetic polymers. Pentaerythritol tetranitrate, PETN, is widely used in blasting caps and detonation cords, bis(dinitropropyl)acetal/formal, BDNPA/F, azidomethyl-methyloxetane (AMMO) and bis(azidomethyl)oxetane (BAMMO) are commonly used plasticizer ingredients. Azido derivatives of pentaerythritol have been previously described (Frankel et al. U.S. Pat. No. 4,683,086). It was of interest to prepare compounds based on three- and four-carbon units with up to four energetic groups thus producing compounds with a higher proportion of energetic groups per mole than the pentaerythritol derivatives. The structural unit of one of the compounds presented herein, 2-azidomethyl-2-hydroxy-1,3-diazidopropane (compound 2, vide infra), has been incorporated into energetic plasticizers formals and acetals (Rindone et al. U.S. Pat. No. 5,220,039) but the subject alcohol 2-azidomethyl-2hydroxy-1,3-diazidopropane 2 has not previously been prepared.
CAUTION: All organic azides described herein should be considered extremely sensitive explosive compounds and should only be handled with proper safety precautions. 1,3-Diazidoacetone exploded subsequent to purification by distillation and extreme caution is urged in dealing with all the azides.
These compounds are expected to be useful in novel explosive and propellant applications as well as to serve as building blocks for the preparation of novel energetic polymers capitalizing on the high reactivity of the azido groups. As a comparison PETN has four energetic groups on a five-carbon framework whereas some of the compounds described herein have four energetic groups on a four- and a three-carbon unit. They are thus, expected to provide much higher energy upon decomposition. The azido groups in these molecules can be converted to triazole and tetrazole to prepare high nitrogen materials of interest in gas generating applications. The ability of azido groups to undergo 1,3-dipolar cycloadditions, make these polyazido compounds useful starting materials for polymeric materials synthesis. In addition, the polyazidopolyesters derived form polycarboxylic acids and the alcohol 2-azidomethyl-2-hydroxy-1,3-diazidopropane 2, are of interest as core molecules for the synthesis of dendrimers.
This invention relates to a series of novel compounds having the general structures A and B: including 2-azido-2-azidomethyl-1,3-diazidopropane (1), 2-azidomethyl-2-hydroxy-1,3-diazidopropane (2), 2-azidomethyl-2-nitrato-1,3-diazidopropane (3), 2-azidomethyl-2-nitro-1,3-diazidopropane (4), 2,2-dinitro-1,3-diazidopropane (5), methallyldiazide (6), a dimer of methallyldiazide (6), comprising 3a,8a-Bis-azidomethyl-3a,4,8a,9-tetrahydro-3H,8H-bis[1,2,3]triazolo[1,5-a; 1″, 5″-d]pyrazine (6-Dimer), 1,3-diazidoacetone (7), and 2-Oximido-1,3-diazidopropane (8).
Also shown are reaction intermediates of these compounds, including 2,2-bis(chloromethyl)oxirane (9), and 2,2-bis(azidomethyl)oxirane (10).
In addition, a number of potentially useful energetic compounds have been prepared from the low molecular weight polyazido compounds above, including N-2(azido-1-azidomethyl-ethylidene)-N″-(2,4-dinitrophenyl)-hydrazine (7-DNPH), 1,3-Bis(4-carboxytriazolyl)2,2-dinitropropane (12), Tris(4-carboxytriazolomethyl)methanol (13), Benzene-1,3,5-tricarboxylic acid tris(2-azido-1,1-bisazidomethyl-ethyl)ester (14), Adamantane 1,3,5,7-tetracarboxylic acid tetrakis(2-azido-1,1-bisazidomethyl-ethyl)ester (15), Adamantane carboxylic acid 2-azido-1,1-bisazidomethyl-ethyl)ester (16), cubane 1,3,5,7-tetracarboxylic acid tetrakis (2-azido-1,1-bisazidomethyl-ethyl)ester (17), cubane 1,4-dicarboxylic acid bis(2-azido-1,1-bisazidomethyl-ethyl)ester (18).